N,N-dialkylamino diphenylamines for dyeing keratinic fibers

ABSTRACT

Diphenylamine of the formula   &lt;IMAGE&gt;   wherein R1 and R4 each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-6 carbon atoms, lower alkoxy having 1-6 carbon atoms, amino, lower alkyl amino wherein the alkyl moiety has 1-6 carbon atoms, acylamino, lower carbamylalkyl amino wherein the alkyl moiety has 1-6 carbon atoms, lower hydroxylalkyl amino wherein the alkyl moiety has 1-6 carbon atoms, lower carbalkoxy amino wherein the alkoxy moiety has 1-6 carbon atoms and ureido; R2 and R3 each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-6 carbon atoms, lower alkoxy having 1-6 carbon atoms, acylamino and ureido; R5 and R8 each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-6 carbon atoms and lower alkoxy having 1-6 carbon atoms; and R6 and R7 are lower alkyl having 1-6 carbon atoms, with the proviso that (a) when both R6 and R7 represent methyl (1) one of R1 and R4 must represent a member selected from the group consisting of amino, lower alkyl amino wherein the alkyl moiety has 1-6 carbon atoms, lower carbamylalkyl amino wherein the alkyl moiety has 1-6 carbon atoms, lower hydroxyalkyl amino wherein the alkyl moiety has 1-6 carbon atoms and ureido, or (2) one of R1 and R4 represent acylamino and R2 and R3 are not both hydrogen, and (b) that when both R6 and R7 represent ethyl, R2 and R3 are other than tertiobutyl.

The present invention relates to diphenylamines or N-alkyl leuco indoanilines disubstituted in the 4' position, to their preparation and to their use for dyeing keratinic fibers, and in particular living human hair.

A currently utilized technique for dyeing keratinic fibers, and especially living human hair, comprises applying to the hair, in the presence of an oxidizing agent added at the moment of use (generally hydrogen peroxide), a dye composition comprising a mixture in an appropriate cosmetric support, of compounds belonging to one or the other of the two following classes.

The first class of compounds, generally called "oxidation bases" is principally constituted by paraphenylenediamines or paraaminophenols which, on oxidation, produce para benzoquinonediimines or parabenzoquinonemonoimines.

The second class of compounds, generally called "couplers" include, especially, metaaminophenols, metaacetylaminophenols, metadiamines and metadiphenols. They are compounds, with which the benzoquinone mono- or di-imines, will react to produce dyes called, depending upon their structure, indophenols, indoanilines or indamines.

These dyes, which provide a range of shades of exceptional richness, are primarily characterized by the luminosity and the richness in glints of dyeings or colorations they impart to the fibers dyed therewith.

However, when a complex dye composition is employed, i.e. a composition which includes several bases and several couplers, it is very difficult to foresee in the final shade the contribution of each possible couple of oxidation base and coupler. In other words, on the one hand, it is very difficult at the outset to predict with any exactitude the final shade that will be attained and, on the other hand, for a given dye composition, it is not often easy to be assured of a perfectly reproducible result. These difficulties are increased by the fact that different secondary reactions can modify the final shade, such secondary reactions including, for instance, formation of Bandrowsky base type compounds from the oxidation bases; recondensation of a molecule of an oxidation base on certain indophenols or on certain indoanilines or indamines; and formation of quinones and the like.

Heretofore, it has also been proposed to use in the dyeing of hair, some indoanilines which are well defined compounds and which impart to the hair essentially perfectly reproducible shades.

However, some inconvenience has been experienced in the use of these compounds since they possess only a slight affinity for kerantinic fibers under conventional conditions for dyeing hair.

The present invention relates to leuco derivatives of indoanilines which are colorless compounds and which, when applied in an aqueous solution to fibers to be dyed, are oxidized at the interior of the keratinic fibers so as to give the corresponding indoanilines. These resulting indoanilines are the colored compounds which are directly responsible for the dyeing of the fibers. The colorations thus obtained exhibit fastness and intensity of coloration which are greater than those of dyeings effected by the direct application of indoanilines, because of the enhanced solubility and better keratinic fiber penetration characteristics of the compounds of the present invention.

The oxidation of leuco derivatives of the present invention to indoanilines can be effected by the oxygen in air or by the use of an oxidizing agent incorporated into the dye composition at the moment of use. Representative oxidizing agents include hydrogen peroxide, urea peroxide and ammonium persulfate.

While the use of the leuco derivatives of indoanilines for dyeing hair has already been proposed, the present invention enlarges the family of such leuco derivatives. Thus the leuco derivatives of indoanilines or diphenylamines of the present invention have the formula ##STR2## wherein R₁ and R₄ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, amino, lower alkyl amino, acylamino, lower carbamylalkyl amino, lower hydroxyalkyl amino, lower carbalkoxy amino and ureido;

R₂ and R₃ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, acylamino and ureido;

R₅ and R₈ each independently represent a member selected from the group consisting of halogen, lower alkyl and lower alkoxy; and

R₆ and R₇ represent lower alkyl with the proviso that (a) when both R₆ and R₇ represent methyl, (1) one of R₁ and R₄ must represent a member selected from the group consisting of amino, lower alkyl amino, lower carbamylalkyl amino, lower hydroxyalkyl amino and ureido, or (2) one of R₁ and %₄ represent acylamino and R₂ and R₃ are not both hydrogen; and (b) that when both R₆ and R₇ represent ethyl, R₂ and R₃ are other than tertiobutyl.

The terms lower alkyl and lower alkoxy mean alkyl and alkoxy containing 1-6 carbon atoms, preferably 1-4 carbon atoms.

The presence of alkyl substituents as R₆ and R₇ results in shifting the colors obtained towards the blues.

The present invention also relates to diphenylamines of formula (I) in the form of their salts such as, for instance, the hydrochlorides, hydrobromides, sulfates and phosphates thereof.

The diphenylamines of formula (I) are the leuco derivatives of indoanilines of formula (II) ##STR3## wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ have the meansing given above.

The indoanilines of formula (II)can be prepared by the condensation of a substituted aniline of formula (III) ##STR4## wherein Z represents NO or NH₂ and r₅, R₆, R₇ and R₈ have the meanings given above, or a salt thereof, on a phenolic compound of the formula (IV) ##STR5## wherein R₁, R₂, R₃ and R₄ have the meanings given above, or a salt thereof.

When Z represents --NH₂, the condensation is carried out in an aqueous, hydroalcoholic or hydroacetonic medium, at an alkaline pH generally greater than 8, in the presence of an oxidizing agent such as, for example, ammonium persulfate, potassium ferricyanide and hydrogen peroxide and at a temperature ranging generally between about 0° to 25° C. The alkaline pH is obtained by the addition to the reaction medium of ammonia or an alkaline carbonate such as sodium carbonate.

The molar ratio of substituted phenol to substituted aniline can range between about 1:0.5 to 1:1.2 and is, preferably about 1:1. The molar ratio of oxidizing agent to substituted phenol ranges from about 1:1 to 4:1 and is preferbly between about 1:1 and 2:1 when ammonium persulfate is employed as the oxidizing agent. This molar ratio is about 8:1 when hydrogen peroxide is employed as the oxidizing agent. Hydrogen peroxide is usually used in the form of a 6 weight percent solution thereof. The reaction medium can be water, a lower alkanol which preferably is ethanol, propanol of isopropanol, an acetone-water mixture or a lower alkanol-water mixture wherein said mixtures the ratio of acetone or alkanol to water ranges between about 1:3 to 2:1.

When Z represents --NO the condensation is generally carried out at a temperature ranging between about 30° to 60° C, preferably 40° to 55° C, in an ethanol-water mixture, preferably a 1:1 mixture thereof, which is either neutral or has been made alkaline by the addition thereto of a dilute solution of sodium hydroxide. The condensation is carried out in the absence of an oxidizing agent.

The reduction of the indoanilines (benzoquinoneimines) of Formula II is carried out using an alkaline hydrosulfite, preferably sodium hydrosulfite, in the presence of sodium hydroxide or acetic acid. Alternatively the reduction can be effected using an alkaline sulfide preferably ammonium sulfide or by catalytic hydrogenation in the presence of a palladium on charcoal catalyst.

According to a first advantgeous method of reducing the indoanilines, excess sodium hydrosulfite is dissolved in an aqueous solution of IN NaOH. To the resulting solution there is added, over a period of about 15 to 30 minuts, while stirring the mixture and maintaining the temperature thereof between about 0° to 30° C, the benzoquinoneimine in solution or suspension in ethanol.

Agitation of the resulting mixture is continued until the solution becomes colorless which generally requires between about 15-60 minutes. The desired diphenylamine (leuco indoaniline) is precipitated by cooling the reaction mixture to 0° C. For certain diphenylamines it is, moreover, necessary to acidify the solution, for example by the addition thereto of acetic acid (see Examples 4, 5, 9, 10, 11, 13 and 14 infra) or of carbonic gas (see Example 12 infra). Cooling to 0° C is effected with the use of ice or solid carbondioxide, the latter serving both to cool the reaction mixture and to acidify the same (see Examples 7, 8 and 15 infra).

According to a second method of reducing the benzoquinoneimines, the benzoquinonemine is dissolved in ethanol (95° titer). To the resulting solution there is added, at ambient temperature, a solution of ammonia saturated with hydrogen sulfide. The desired diphenylamine is precipitated by the addition thereto of water (see Example 6, infra).

The diphenylamine of Example 3, below, has been prepared in accordance with a third method according to which excess sodium hydrosulfite is dissolved in a 10% aqueous solution of acetic acid. To this solution, maintained at a temperature between about 15°-20° C, there is added, while stirring the same, the benzoquinoneimine in the form of an ethanol solution thereof. Stirring is continued until the solution becomes colorless which is effected in proportion to the addition of the benzoquinoneimine. The solution is then neutralized with ammonia to the point of the precipitation of the diphenylamine in crystalline form which precipitation occurs at a pH of about 5 to 7.5.

According to a fourth method of reducing the benzoquinoneimines, as seen for instance in Examples 1 and 2 below, 0.004 mole of benzoquinoneimine is partially dissolved in 150 ml of absolute ethanol. There is then added thereto 0.2 g of palladium on charcoal (10 weight percent palladium) as a catalyst and the indoaniline is reduced by hydrogenation under atmospheric pressure. The reaction mixture is then filtered to recover the catalyst after which the remaining mixture is concentrated under a vacuum and under a nitrogen atmosphere. The desired diphenylamine is then precipitated in the form of crystals by the addition of ice water or in the form of a salt by the addition of an acid.

The diphenylamines of the present invention are usefully employed for dyeing keratinic fibers and, in particular, living human hair.

These diphenylamines, when applied to hair in an aqueous or hydroalcoholic solution, at a concentration ranging between about 0.002 to 5 weight percent thereof, and preferbly between 0.02 to 3 weight percent, provide, after oxidation, either with air or by another oxidizing agent such as hydrogen peroxide, urea peroxide or ammonium persulfate, a range of shades which are very rich in the area of pinks to violets, blues and greens. Additionally, the diphenylamines of the present invention provide some very luminous grays and beiges which are rich in glints.

The present invention also relates to a composition for dyeing keratinic fibers, particularly living human hair, comprising an aqueous solution or hydroalcoholic solution, preferably hydroethanolic or hydroisopropanolic, of at least one diphenylamine of Formula (I) wherein R₁ and R₄ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, amino, lower alkyl amino, acylamino, lower carbamylalkyl amino, lower hydroxyalkyl amino, lower carbalkoxy amino and ureido; R₂ and R₃ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, acylamino and ureido; R₅ and R₈ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy; and R₆ and R₇ represent lower alkyl. As indicated above, said lower alkyl and lower alkoxy groups or moieties contain 1-6 and preferably 1-4 carbon atoms.

The dye composition of the present invention can also include a salt of the diphenylamines of Formula (I) and in particular the hydrochloride, hydrobromide, sulfate or phosphate thereof.

The dye compositions according to the present invention can include as the active dyeing agent only the compounds of formula (I). However, they can also include other known leuco derivatives of indoanilines, indamines or indophenols, or even oxidation dyes such as ortho- or para-phenylenediamines or ortho- or para-aminophenols, as well as benzene compounds trisubstituted or tetrasubstituted by hydroxy, amino or alkoxy groups and couplers such as metadiamines, metadiphenols, metaaminophenols, metaacetylaminophenols or even direct dyes such as nitrobenzene dyes, azo dyes or anthraquinone dyes, indoanilines, indamines and/or indophenols.

The compositions according to the present invention are generally provided in the form of an aqueous or hydroalcoholic solution containing one or more compounds of formula (I), in admixture or not with other dyes. They can, however, also include thickening agents and be provided in the form of a cream or gel.

Representtive thickening agents that can be incorporated into the dye composition of the present invention include cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or acrylic polymers such as the sodium salt of polyacrylic acid or carboxyvinyl polymers.

The dye composition can containas solvents, water, lower alkanols for example ethanol or isopropanol, polyalcohols such as glycols,for example, ethylene glycol, propylene glycol, butyl glycol, diethyleneglycol and the monomethyl ether of diethylene glycol.

The dye composition according to the present invention can also include other components generally employed in cosmetics, such as surface active agents used as carriers, as thickening agents, as dispersants or as wetting agents; swelling agents; penetrating agents; emollients; polymers and/or perfumes. The composition of the present invention can also be packaged in aerosol containers together with an aerosol propellant.

Representative surface active agents include oxyethylenated alcoholes and particularly oxyethylenated lauryl alcohol, partially sulfated oxyethylenated lauryl alcohol and preferably a mixture of 19% partially sulfated lauryl alcohol oxyethylenated with 2 moles of ethylene oxide and 81% of the sodium sulfate salt of this same oxyethylenated alcohol, the alkaline salts or ammonium sulfates of long chain fatty alcohols for example, ammonium lauryl sulfate, oxyethylenated alkylphenols and preferably nonylphenol oxyethylenated with 4 or 9 moles of ethylene oxide per mole of alkylphenol, oxyethylenated fatty acids and the sulfates and sulfonates of fatty alcohols optionally oxyethylenated.

Representative aerosol propellants usefully employed in compositions according to the present invention include nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane or propane, or preferably fluorinated hydrocarbons (sold under the name of Freon by Dupont) such as as dichlorodifluoromethane, 1,1-difluoromethane, 1,2-dichloro-1,1,2,3-tetrafluoroethane and 1-chloro-1,1-difluoromethane. Mixtures of two or more hydrocarbons or fluorinated hydrocarbons can also be used.

The pH of the compositions of the present invention can vary widely and generally it rages between about 4.5 to 12 and preferbly between about 6.5 and 10.5.

The pH of the composition can be adjusted with the aid of an alkalizing agent such as, for example, ammonia, mono-, di- or tri-ethanolamine, di- or tri-sodium phosphate, sodium carbonate or potassium carbonate, or with the aid of an acidifying agent such as, for example, acetic acid, lactic acid, phosphoric acid or citric acid.

The dyeing of kertinic fibers and, in particular, living human hair, with the use of the dye compositions of the present invention, is carried out in a conventional manner by applying the said composition to the fibers to be dyed, permitting said composition to remain in contact with the fibers for a period of time ranging from about 5 to 30 minutes, rinsing and optionally washing the fibers and then drying the fibers. Prior to applying the said composition to the fibers there can be added to said composition an oxidizing agent such as 30 to 100 percent by volume of hydrogen peroxide, generally 6% (20 volumes), or0.1 to 15% by weight of an oxidizing agent such as urea peroxide or ammonium persulfate.

The compositions according to the present invention, when present in the form of a hydroalcoholic solution, can also include a cosmetric resin, so as to provide a colored hair setting lotion, which can be applied to wet or moist hair before setting.

Representative cosmetic resins that can be used in the hair setting lotion composition of the present invention include such film-forming polymers as polyvinylpyrrolidone; copolymers of polyvinylpyrrolidone and vinyl acetate; copolymers of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid; copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and an acrylic or methacrylic ester; copolymers resulting from the copolymerization of vinyl acetate and a vinyl alkyl ether; copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and a vinyl ester of a long carbon chain acid or even of an allyl or methallyl ester of a long carbon chain acid; copolymers resulting from the copolymerization of an ester derived from an unsaturated alcohol and a short carbon chain acid, of an unsaturated short carbon chain acid and of at least one ester derived from a short carbon chain saturated alcohol and an unsaturated acid; and copolymers resulting from the copolymerization of at least one unsaturated ester and at least one unsaturated acid.

Representative preferred cosmetic resins include polyvinylpyrrolidone having a molecular weight ranging between about 10,000 to 360,000; copolymers of 10% crotonic acid and 90% vinyl acetate having a molecular weight ranging between about 10,000 of 70,000; copolymers of vinylpyrrolidone and vinyl acetate having a molecular weight ranging between about 30,000 to 200,000 wherein the ratio of VP to VA ranges between 30:70 to 70:30; copolymers of maleic anhydride and methyl vinyl ether in a 1 to 1 molar ratio, having a specific viscosity, measured at 25°C and at a concentration of 1 g in 100 ml of methylethylketone ranging between about 0.1 and 3.5; the monoethyl, monoisopropyl and monobutyl esters of said maleic anhydride-methyl vinyl ether copolymers; copolymers of maleic anhydride and vinylbutyl either in a 1 to 1 molar ratio; terpolymers of methyl methacrylate (15-25%) stearyl methacrylate (25-35%) and dimethylaminoethyl methacrylate (52-62%), preferably quaternized for example by dimethyl sulfate, and the viscosity of which, measured at the boiling point of the ether and at a concentration of 5% in dimethylformamide, ranges between about 8-12 centipoises and terpolymers of vinyl acetate (75-85%), allyl stearate (10-20%) and allyloxy acetic acid (3-10%), the viscosity of which, measured at the boiling point of ether and at a concentration of 5% in dimethylformamide ranges between about 4.4 and 5 centipoises.

These cosmetic film-forming resins are used generally in an amount between about 1-3 percent by weight of the total hair setting lotion composition.

The alcohols generally employed in the production of the hair setting lotion compositions of the present invention are low molecular weight alcohols, preferably ethanol or isopropanol. These alcohols are used in an amount of about 20 to 70 weight percent of the total composition.

The hair setting lotion composition of the present invention can be utilized in a conventional manner by applying the same to wet or moist hair, previously washed and rinsed, followed by rolling the hair up on curlers and drying the hair.

The present invention is illustrated by the following non-limiting examples. These examples are tabulated in Tables I, I-bis, II, III and IV.

Examples of preparing the diphenylamines of the present invention appear in Tables I, I-bis and II. Table I, which indicates the characteristics of the prepared diphenylamines, has 9 columns numbered (1) through (9). Column (1) indicates the number of the example of preparation; the name of the compound prepared appears in column (2); columns (3) and (4) indicate, respectively, the melting point and the empirical formula; columns numbered (5) through (9) indicate, respectively, the percentages of C, H, N, Cl and S. For each compound prepared, columns (5) through (9) carry two to three lines, the first line indicating the theoretical percentages corresponding to the empirical formula of column (4), while the second and third lines indicate the percentages found by analysis.

Table I-bis indicates the characteristics of the benzoquinoneimines (indoanilines) which serve as an initial reactant in the preparation of the diphenylamines appearing in Table I. Table I-bis carries the same columns as Table I.

Table II, which indicates the manner in which the benzoquinoneimines appearing in Table I-bis are prepared, includes eight columns. Column (1) indicates, as in Table I, the number of the example of preparation. The columns following are numbered (11) through (17). Columns (11) and (12) indicate the name of the initial reactants, i.e. the substituted aniline in column (11) and substituted phenol in column (12). Column 13 entitled "ratio of (12):(11)" indicates the molar ratio between the substituted phenol and substituted aniline initial reactants.

Column (14) indicates the reaction medium; column (15), the nature of the oxidizing agent used; column (16) entitled "ratio of (15):(12)" indicates the molar ratio between the oxidizing agent and the substituted pheonol; and column (17) indicates the reaction temperature in Centigrade degrees.

The examples of use include examples of simple dye compositions as well as dye compositions which also include a cosmetic resin and are called hair setting lotions. All examples of use are tabulated in Table III.

Table III carries 13 columns numbered (31) to (43). Column (31) indicates the number of the example of use. This column carries a number preceded by the letter A. Column (32) carries a figure which corresponds to a number appearing in column (1) of table I and indicates the diphenylamine used, or carries the letter C followed by a number which represents another dye used in admixture with the diphenylamine. The name of this dye appears at the bottom of the Table. Column (33) indicates the quantity of dye, expressed in percent by weight of the total weight of the composition. Columns (34) and (35) indicate, respectively, the nature and the weight percent of adjuvants used, based on the total weight of the simple dye composition or the hair setting lotion composition. In these columns appear the surface active agent, the thickening agent, the cosmetic polymer and all other components used in the dye composition and hair setting lotion composition.

Columns (36) and (37) indicate, respectively, the nature and the percent by weight of the total weight of the composition, of the solvent used other than water. The percent by weight of water used represents the difference between 100 g and the total weight appearing in columns (33), (35) and (37).

Columns (38), (39) and (40) indicate, respectively, the nature, the volume (expressed in ml) and the concentration of the solution of the oxidizing agent added to 100 g of the composition.

Column (41) indicates the pH of the composition while column (43) indicates the color obtained on bleached hair (D) or on 95% naturally white hair (B 95), this latter indication appearing in column (42).

In columns (32), (34), (36) and (38), there appear the names, respectively, of dyes other than the diphenylamines of the present invention, the adjuvants which include the polymers, the solvents and the oxidizing agents. These indications are given by abbreviations, for which the meanings, and in the case of the polymers, such characteristics as molecular weight or viscosity, appear at the bottom of the Tables. Unless indicated to the contrary, all percentages are by weight of the total weight of the dye composition or the hair setting lotion composition.

                                      TABLE I                                      __________________________________________________________________________                                              ANALYSIS                              Ex.                        M.P.  EMPIRICAL                                                                              C    H   N    Cl   S                  No.                                                                               DIPHENYLAMINES          (C°)                                                                          Formula %    %   %    %    %                  (1)                                                                                 (2)                   (3)    (4)    (5)  (6) (7)  (8)  (9)                __________________________________________________________________________      1  3-methyl-4-hydroxy-6-amino-4'-dimethylamino                                                           170  C.sub.15 H.sub.19 N.sub.3 O                                                             70.03                                                                               7.39                                                                               16.34                            diphenylamine               M.W. = 257 (a)                                                                          69.75                                                                               7.58                                                                               16.44                                                        M.W. = 263 (b)                                                                          69.82                                                                               7.50                                                                               16.38                         2  3,5-dimethyl-2-amino-4-hydroxy-4'-dimethylamino                                                       220  C.sub.16 H.sub.24 O N.sub.3 Cl.sub.3                                                    50.46                                                                               6.37                                                                               11.04                                                                               27.94                       diphenylamine trihydrochloride       50.31                                                                               6.24                                                                               10.97                                                                               27.74                                                            50.29                                                                               6.32                                                                               11.03                                                                               27.69                    3  4-hydroxy-3-methyl-6-ureido-4'-N,N-dimethyl-                                                          260  C.sub.16 H.sub.20 N.sub.4 O.sub.2                                                       63.98                                                                               6.71                                                                               18.65                            amino diphenylamine                  63.60                                                                               6.84                                                                               18.58                                                                 63.63                                                                               6.82                                                                               18.45                         4  3,5-dimethyl-4-hydroxy-2-acetylamino-4'-N,N-                                                          204  C.sub.18 H.sub.23 N.sub.3 O.sub.2                                                       69.01                                                                               7.35                                                                               13.41                            dimethylamino diphenylamine          68.73                                                                               7.47                                                                               13.34                                                                 68.81                                                                               7.35                                                                               13.35                         5  3-methyl-4-hydroxy-6-carbamylmethylamino-                                                             148  C.sub.23 H.sub.34 N.sub.4 O.sub.                                                        69.31                                                                               8.60                                                                               14.06                            4'-N,N-dibutylamino diphenylamine    69.30                                                                               8.53                                                                               14.12                                                                 69.76                                                                               8.43                                                                               14.17                         6  2-chloro-4-hydroxy-5-ureido-2'-methyl-4'-N,N-                                                         194  C.sub.18 H.sub.23 N.sub.4 O.sub.2                                                       59.58                                                                               6.34                                                                               15.42                                                                                9.79                       diethylamino diphenylamine           59.33                                                                               6.47                                                                               15.44                                                                                9.61                                                            59.05                                                                               6.59                                                                               15.43                                                                                9.69                    7  3,5-dimethyl-2-amino-4-hydroxy-4'-N,N-diethyl-                                                         92  C.sub.18 H.sub.24 N.sub.3 O                                                             64.77                                                                               7.28                                                                               12.59                                                                               10.64                       amino-2'-chloro diphenylamine        64.50                                                                               7.17                                                                               12.65                                                                               10.54                    8  3,6-dimethyl-4-hydroxy-4'-N,N-dimethylamino                                                           140  C.sub.16 H.sub.20 N.sub.2 O                                                             74.96                                                                               7.86                                                                               10.93                            diphenylamine                        74.72                                                                               7.71                                                                               10.86                         9  3,5-dimethyl-4-hydroxy-2-amino-4'-N,N-dimethyl-                                                       153  C.sub.17 H.sub.23 N.sub.2 O.sub.2                                                       67.75                                                                               7.69                                                                               13.94                            amino-2'-methoxy diphenylamine       67.71                                                                               7.54                                                                               14.04                        10  3-methoxy-4-hydroxy-6-acetylamino-4'-N,N-di-                                                          202  C.sub.17 H.sub.21 N.sub.3 O.sub.3                                                       64.76                                                                               6.67                                                                               13.33                            methylamino diphenylamine            64.84                                                                               6.50                                                                               13.57                        11  3,3'-dichloro-4-hydroxy-6-acetylamino-4'-N,N-                                                         236  C.sub.16 H.sub.17 N.sub.3 O.sub.2                                              Cl.sub.2 54.24                                                                               4.85                                                                               11.86                            dimethylamino diphenylamine          53.96                                                                               4.90                                                                               11.91                        12  3,5,2',6'-tetramethyl-4-hydroxy-2-ureido-4'-N,                                                        <260 C.sub.19 H.sub.26 N.sub.4 O.sub.2                                                       66.64                                                                               7.65                                                                               16.36                            N-dimethylamino diphenylamine                                                                         with de-      66.45                                                                               7.48                                                                               16.12                                                   composi-                                                                       tion                                                13  3-methyl-4-hydroxy-6-carbamylmethylamino-4'-                                                          218  C.sub.18 H.sub.24 N.sub.4 O.sub.2                                                       65.83                                                                               7.37                                                                               17.06                            N,N-dimethylamino-3'-methyl diphenylamine                                                                           66.10                                                                               7.54                                                                               16.86                        14  3-methyl-4-hydroxy-6-β-hydroxyethylamino-2'-                                                     135  C.sub.17 H.sub.22 N.sub.3 O.sub.2                                                       60.80                                                                               6.56                                                                               12.52                            chloro-4'-N,N-dimethylamino diphenylamine                                                                           60.53                                                                               6.47                                                                               12.77                        15  3-methyl-4-hydroxy-6-carbethoxyamino-4'-N,N-di-                                                       172  C.sub.18 H.sub.22 N.sub.3 O.sub.3                                                       59.42                                                                               6.05                                                                               11.55                            methylamino-3'-chloro diphenylamine  59.14                                                                               6.09                                                                               11.72                        16  3-methyl-4-hydroxy-6-acetylamino-3'-chloro-4'-                                                        208  C.sub.17 H.sub.20 N.sub.3 O.sub.2                                                       61.17                                                                               6.00                                                                               12.59                                                                               10.64                       N,N-dimethylamino diphenylamine      61.07                                                                               6.08                                                                               12.44                                                                               10.63                   17  3,5-dimethyl-4-hydroxy-2-acetylamino-3'-chloro-                                                       205  C.sub.18 H.sub.22 N.sub.3 O.sub.2                                                       62.16                                                                               6.35                                                                               12.09                            4'-N,N-dimethylamino diphenylamine   62.13                                                                               6.41                                                                               12.20                        18  3,5,2',6'-tetramethyl-4-hydroxy-2-acetylamino-                                                        260  C.sub.20 H.sub.27 N.sub.3 O.sub.2                                                       70.35                                                                               7.97                                                                               12.31                            4'N,N-dimethylamino diphenylamine    69.92                                                                               7.96                                                                               11.99                        19  3,2',6'-trimethyl-4-hydroxy-6-amino-4'-N,N-di-                                                        189  C.sub.17 H.sub.23 N.sub.3 O                                                             71.54                                                                               8.12                                                                               14.73                            methylamino diphenylamine            71.80                                                                               8.33                                                                               14.79                        20  3,2'-dimethyl-4-hydroxy-6-carbamylmethyl-amino-                                                       201  C.sub.18 H.sub.24 N.sub.4 O.sub.2                                                       65.83                                                                               7.37                                                                               17.06                            4'-N,N-dimethylamino diphenylamine   65.91                                                                               7.35                                                                               17.29                        21  3,5-dimethyl-4-hydroxy-3'-chloro-4'-N,N-dimethyl-                                                      97  C.sub.16 H.sub.19 N.sub.2 O                                                             66.09                                                                               6.54                                                                                9.63                            amino diphenylamine                  66.05                                                                               6.46                                                                                9.60                        22  3,5,2',6'-tetramethyl-4-hydroxy-4'-N,N-dimethyl-                                                      140  C.sub.18 H.sub.24 N.sub.2 O                                                             76.02                                                                               8.51                                                                                9.85                            amino diphenylamine                  75.98                                                                               8.64                                                                                9.66                        __________________________________________________________________________      (a) molecular weight calculated                                                (b) molecular weight found by potentiometric titration in acetic acid wit      a 0.1 N solution of perchloric acid.                                     

                                      TABLE I - bis                                __________________________________________________________________________                                                 ANALYSIS                           Ex.                        M.P.             C    H  N   Cl  S                  No.                                                                               BENZOQUINONEIMINES      (C°)                                                                        EMPIRICAL FORMULA                                                                           %    %  %   %   %                  (1)                                                                                  (2)                  (3)    (4)       (5)  (6)                                                                               (7) (8) (9)                __________________________________________________________________________      1 N-[(4'-(dimethylamino)phenyl] 6-methyl-3-amino                                                         255 C.sub.15 H.sub.17 N.sub.3 O                                                                 70.58                                                                               6.66                                                                              16.47                         benzoquinoneimine                        70.45                                                                               6.82                                                                              16.34                       2 N-[4'-(dimethylamino)phenyl] 2,6-dimethyl-3-                                                           178 C.sub.16 H.sub.19 N.sub.3 O                                                                 71.34                                                                               7.11                                                                              15.60                         amino benzoquinoneimine                  71.41                                                                               7.19                                                                              15.45                                                                  71.57                                                                               7.26                                                                              15.57                       3 N-[4'-(dimethylamino)phenyl] 2-methyl-5-ureido                                                         275 C.sub.16 H.sub.18 N.sub.4 O.sub.2                                                           64.41                                                                               6.37                                                                              18.78                         benzoquinoneimine                        64.29                                                                               6.21                                                                              19.01                                                                  64.44                                                                               6.26                                                                              18.93                       4 N-[4'-(dimethylamino)phenyl] 2,6-dimethyl-3-                                                           111 C.sub.18 H.sub.21 N.sub.3 O.sub.2                                                           69.43                                                                               6.80                                                                              13.50                         acetylamino benzoquinoneimine            69.13                                                                               6.64                                                                              13.72                                                                  69.25                                                                               6.74                                                                              13.60                       5 N-[4'-(dibutylamino)phenyl] 2-methyl-5-carba-                                                          169 C.sub.23 H.sub.32 N.sub.4 O.sub.                                                            69.66                                                                               8.13                                                                              14.13                         mylmethylamino benzoquinoneimine         69.80                                                                               8.23                                                                              14.04                                                                  69.68                                                                               8.26                                                                              13.98                       6 N-[(4'-diethylamino-2'-methyl)phenyl] 3-chloro-                                                        225 C.sub.18 H.sub.21 N.sub.4 O.sub.2 Cl                                                        59.91                                                                               5.83                                                                              15.53                                                                               9.84                     6-ureido benzoquinoneimine               59.27                                                                               5.72                                                                              15.36                                                                               9.75                                                              59.36                                                                               5.66                                                                              15.41                                                                              10.00                   7 N-[(4'-diethylamino-2'-chloro)phenyl] 2,6-di-                                                          160 C.sub.18 H.sub.22 N.sub.3 O                                                                 65.15                                                                               6.65                                                                              12.67                                                                              10.70                     methyl-3-amino benzoquinoneimine         65.04                                                                               6.72                                                                              12.73                                                                              10.84                                                              65.14                                                                               6.74                                                                              12.69                                                                              10.92                   8 N-[(4'-dimethylamino)phenyl] 2,5-dimethyl                                                              127 C.sub.16 H.sub.18 N.sub.2 O                        benzoquinoneimine           M.W. = 254 (a)                                                                 M.W. = 254 (b)                                   9 N-[(4'-dimethylamino-2'-methoxy)phenyl]2,6-                                                            152 C.sub.17 H.sub.21 N.sub.3 O.sub.2                                                           68.20                                                                               7.07                                                                              14.04                         dimethyl-3-amino benzoquinoneimine       68.09                                                                               7.21                                                                              14.23                      10 N-[4'-(dimethylamino)phenyl] 2-methoxy-5-ace-                                                          251 C.sub.17 H.sub.19 N.sub.3 O.sub.3                                                           65.18                                                                               6.07                                                                              13.42                         tylamino benzoquinoneimine               64.97                                                                               6.20                                                                              13.22                      11 N-[(4'-dimethylamino-3'-chloro)phenyl] 2-chloro-                                                       195 C.sub.16 H.sub.15 N.sub.3 O.sub.2 Cl.sub.2                                                  54.54                                                                               4.30                                                                              11.93                         5-acetylamino benzoquinoneimine          54.46                                                                               4.42                                                                              11.64                      12 N-[(4'-dimethylamino-2',6'-dimethyl)phenyl]                                                            240 C.sub.19 H.sub.24 N.sub.4 O.sub.2                                                           67.03                                                                               7.11                                                                              16.46                         2,6-dimethyl-3-ureido benzoquinoneimine                                                                de-              66.92                                                                               7.00                                                                              16.68                                                 com-                                                                           posi-                                                                          tion                                                13 N-[(4'-dimethylamino-3'-methyl)phenyl] 2-methyl-                                                       214 C.sub.18 H.sub.22 N.sub.4 O.sub.2                                                           66.23                                                                               6.79                                                                              17.17                         5-carbamylmethylamino benzoquinoneimine  66.13                                                                               6.65                                                                              17.44                      14 N-[(4'-dimethylamino-2'-chloro)phenyl] 6-methyl-                                                       176 C.sub.17 H.sub.20 N.sub.3 O.sub.2 Cl                                                        61.17                                                                               5.99                                                                              12.60                                                                              10.65                     3-(β-hydroxyethylamino) benzoquinoneimine                                                                          60.94                                                                               6.10                                                                              12.51                                                                              10.60                  15 N-[(4'-dimethylamino-3'-chloro)phenyl] 6-methyl-                                                       142 C.sub.18 H.sub.20 N.sub.3 O.sub.3 Cl                                                        59.75                                                                               5.54                                                                              11.62                                                                               9.82                     3-carbethoxy amino benzoquinoneimine     59.81                                                                               5.69                                                                              11.55                                                                               9.89                  16 N-[(4'-dimethylamino-3'-chloro)phenyl] 6-methyl-                                                       156 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl . 0.5                                     H.sub.2 O    59.91                                                                               5.62                                                                              12.33                                                                              10.40                     3-acetylamino benzoquinoneimine, semi-hydrate                                                                           59.87                                                                               5.60                                                                              12.38                                                                              10.52                  17 N-[(4'-dimethylamino-3'-chloro)phenyl] 2,6-di-                                                         136 C.sub.18 H.sub.20 N.sub.3 O.sub.2 Cl                                                        62.52                                                                               5.82                                                                              12.15                                                                              10.25                     methyl-3-acetylamino benzoquinoneimine   62.54                                                                               5.95                                                                              12.24                                                                              10.42                  18 N-[(4'-(dimethylamino)2,6' -dimethyl)phenyl]                                                           194 C.sub.20 H.sub.25 N.sub.3 O.sub.2                                                           70.77                                                                               7.43                                                                              12.38                         2,6-dimethyl-3-acetylamino benzo-        70.86                                                                               7.26                                                                              12.22                         quinoneimine                                                                19 N-[(4'-dimethyl amino)2',6'-dimethyl)phenyl]                                                           226 C.sub.17 H.sub.21 N.sub.3 O                                                                 72.05                                                                               7.47                                                                              14.83                         2-methyl-5-amino benzoquinoneimine       72.18                                                                               7.46                                                                              14.96                      20 N-[(4'-dimethylamino-2'-methyl)phenyl] 2-methyl-                                                       218 C.sub.18 H.sub.22 N.sub.4 O.sub.2 . 0.5                                        H.sub.2 O    64.47                                                                               6.86                                                                              16.71                         5-carbamylmethylamino benzoquinoneimine semi-                                                                           64.62                                                                               6.91                                                                              16.76                         hydrate                                                                     21 N-[(4'-dimethylamino-3'-chloro)phenyl] 2,6-di-                                                          62 C.sub.16 H.sub.17 N.sub.2 O                                                                 66.19                                                                               5.58                                                                               9.70                                                                              12.27                     methyl benzoquinoneimine                 66.39                                                                               5.73                                                                               9.87                                                                              12.47                  22 N-[(4'-dimethylamino-2',6'-dimethyl)phenyl]                                                            152 C.sub.18 H.sub.22 N.sub.2 O.sub.2                                                           76.56                                                                               7.85                                                                               9.92                         2,6-dimethyl benzoquinoneimine           76.45                                                                               7.72                                                                              10.01                      __________________________________________________________________________      (a) molecular weight calculated                                                (b) molecular weight found by potentiometric titration in acetic acid wit      a 0.1 N solution of perchloric acid.                                     

                                      TABLE II                                     __________________________________________________________________________     Ex.                                   Ratio of                                                                            Reaction                                                                              Oxidizing                                                                           Ratio                                                                               Temp.              No.                                                                               SUBSTITUTED ANILINE     SUBSTITUTED PHENOL                                                                        (12) : (11)                                                                         Medium Agent                                                                               (15) :                                                                              (° C)       (1)                                                                                  (11)                   (12)     (13) (14)   (15) (16) (17)               __________________________________________________________________________      1 N,N-dimethyl paraphenylene diamine dihydro-                                                            2-methyl-5-amino                                                                          1 : 1                                                                               acetone-water                                                                         ammonium                                                                            1 :                                                                                 5                     chloride                phenol          1:2    persulfate                    2 N,N-dimethyl paraphenylenediamine dihydro-                                                             2,6-dimethyl-3-amino                                                                      1 : 1                                                                               acetone-water                                                                         "    1.1 : 1                                                                             0                     chloride                                1:2                                  3 N,N-dimethyl paraphenylenediamine dihydro-                                                             2-methyl-5-ureido                                                                         1 : 1                                                                               isopropanol-                                                                          "    2 :                                                                                 0                     chloride                phenol          water 1:2                            4   "                     2,6-dimethyl-3-ace-                                                                       1 : 1                                                                               acetone-water                                                                         "    2 :                                                                                 10                                            tylamino phenol 1:2                                  5 4-nitroso N,N-dibutylaniline hydrochloride                                                             2-methyl-5-carbamyl-                                                                      1 : 1                                                                               ethanol-water    40                                            methylamino phenol                                                                             1:1                                  6 2-methyl-4-N,N-diethylamino aniline hydro-                                                             3-chloro-6-ureido                                                                         1 : 1                                                                               isopropanol-                                                                          "    1 :                                                                                 0                     chloride                phenol          water 1:1                            7 3-chloro-4-nitroso diethylaniline                                                                      2,6-dimethyl-3-amino                                                                      1.1 : 1                                                                             ethanol-water    35                                            phenol hydrochloride                                                                           1:1                                  8 N,N-dimethyl-paraphenylene diamine dihydro-                                                            2,5-dimethyl phenol                                                                       1 : 1                                                                               acetone-water                                                                         ammonium                                                                            2 :                                                                                 0-5                   chloride                                       persulfate                    9 3-methoxy-4-nitroso N,N-dimethylaniline                                                                2,6-dimethyl-5-amino                                                                      1.1 : 1                                                                             ethanol-water    50                                            phenol hydrochloride                                                                           1:2.5                               10 N,N-dimethyl paraphenylenediamine dihydro-                                                             2-methoxy-5-acetyl-                                                                       1 : 1                                                                               acetone-water                                                                         ammonium                                                                            2 :                                                                                 0                     chloride                amino phenol    1:3    persulfate                   11 2-chloro-4-amino N,N-dimethylaniline                                                                   2-chloro-5-acetylamino                                                                    1 : 1                                                                               water  ammonium                                                                            2 :                                                                                 10                                            phenol                 persulfate                   12 3,5-dimethyl-4-amino N,N-dimethylaniline di-                                                           2,6-dimethyl-3-ureido                                                                     1 : 1                                                                               acetone-water                                                                         "    2 :                                                                                 10                    hydrochloride           phenol          1:1                                 13 2-methyl-4-amino N,N-dimethylaniline                                                                   2-methyl-5-carbamyl-                                                                      1 : 1                                                                               acetone-water                                                                         "    2 :                                                                                 0                                             methylamino phenol                                                                             1:2                                 14 3-chloro-4-amino N,N-dimethylaniline                                                                   2-methyl-5-(N-β-hy-                                                                  1 : 1                                                                               acetone-water                                                                         "    1 :                                                                                 5                     dihydrochloride         droxyethylamino)                                                                               1:2                                                            phenol                                              15 2-chloro-4-amino N,N-dimethylaniline                                                                   2-methyl-5-carbetho-                                                                      1 : 1                                                                               ethanol-water                                                                         "    2 :                                                                                 0                                             xy phenol       2:1                                 16 2-chloro-4-amino N,N-dimethylaniline                                                                   2-methyl-5-acetyl-                                                                        1 : 1                                                                               acetone-water                                                                         "    2 :                                                                                 0                                             amino phenol    1:1                                 17 2-chloro-4-amino N,N-dimethylaniline                                                                   2,6-dimethyl-5-ace-                                                                       1 : 1                                                                               acetone-water                                                                         "    2 :                                                                                 5                                             tylamino phenol 1:1                                 18 3,5-dimethyl-4-amino N,N-dimethylaniline di-                                                           2,6-dimethyl-3-ace-                                                                       1 : 1                                                                               "      "    2 :                                                                                 10                    hydrochloride           tylamino phenol                                     19 "                       2-methyl-5-amino                                                                          1 : 1                                                                               "      "    2 :                                                                                 10                                            phenol                                              20 3-methyl-4-amino N,N-dimethylaniline dihydro-                                                          2-methyl-5-carbamyl-                                                                      1 : 1                                                                               acetone-water                                                                         ammonium                                                                            2 :                                                                                 0                     chloride                methylamino phenol                                                                             1:2    persulfate                   21 2-chloro-4-amino N,N-dimethyl aniline                                                                  2,6-dimethyl phenol                                                                       1 : 1                                                                               1:1    "    2 :                                                                                 0                  22 3,5-dimethyl-4-amino N,N-dimethylaniline                                                               2,6-dimethyl phenol                                                                       1 : 1                                                                               "      "    2 :                                                                                 10                    dihydrochloride                                                             __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________     (31)                                                                              (32)  (33)                                                                              (34)      (35)                                                                              (36)  (37)                                                                             (38) (39)                                                                              (40)                                                                             (41)                                                                               (42)  (43)                      Ex.                                                                               DYE      ADJUVANT     SOLVENT Oxidizing Agent                               No.                                                                               Ex. No.                                                                              %  Nature    %  Nature                                                                               % Nature                                                                              ml conc.                                                                            pH  Hair COLOR                      __________________________________________________________________________     A 1                                                                               7     0.2             Isopropanol                                                                          40                                                                               PU (1)                                                                              100                                                                               10%                                                                              9.7 D (1 bis)                                                                           tamaris pink               A 2                                                                               2     0.15                                                                              AL 10.5 OE (4)                                                                           20         H.sub.2 O.sub.2                                                                     40 6%                                                                               9.5 D    pearly pink grey-             Cl (2)                                                                               0.15                                       beige                         C2 (3)                                                                               0.10                                                                  A 3                                                                               3     1.00                                                                              LSS 19 (5)                                                                               20                   10.7                                                                               D    silvery blue gray                      EDTA (6)  0.2                                                      A 4                                                                               2     0.40                                                                              CMC (10)  5          H.sub.2 O.sub.2                                                                     40 6%                                                                               5.6 B95 (11)                                                                            deep gray with                C.sub.3                                                                           (6a)                                                                              0.40                                       bronze glints                 C.sub.4                                                                           (7)                                                                               0.20                                                                     C.sub.5                                                                           (8)                                                                               0.40                                                                     C.sub.6                                                                           (9)                                                                               0.10                                                                  A 5                                                                               2     1.37                                                                              CMC (10)  10         H.sub.2 O.sub.2                                                                     55 6%                                                                               8.5 D    violet                     A 6                                                                               C.sub.7                                                                           (12)                                                                              2.05            Ethanol                                                                              50          8.75                                                                               B 95 petroleum blue             A 7                                                                               1     0.9             Ethanol                                                                              40                                                                               H.sub.2 O.sub.2                                                                     100                                                                               6%                                                                               9.3 B 95 turtle-dove gray           A 8                                                                               4     0.54                                                                              AL 10.5 OE (4)                                                                           5  Butylglycol                                                                           5          10  B 95 metallic gray              A 9                                                                               C.sub.8                                                                           (13)                                                                              3.0                                                                               LSS 19 (5)                                                                               20                   11.3                                                                               B 95 eucalyptus green                       EDTA (6)  0.2                                                                  40% sodium bi-                                                                 sulfite solution                                                                         1                                                        A 10                                                                              6     0.2                                                                               AL 10.5 OE (4)                                                                           5  Butylglycol                                                                           5                                                                               H.sub.2 O.sub.2                                                                     50 6%                                                                               11  B 95 pink beige with               C.sub.9                                                                           (14)                                                                              0.4                                        golden glints              A 11                                                                              5     0.25                                                                              D.C. (16) 10         H.sub.2 O.sub.2                                                                     50 6%                                                                               12  B 95 golden honey                  C.sub.10                                                                          (15)                                                                              2.5                                                                   A 12                                                                              C.sub.11                                                                          (17)                                                                              0.25                                                                              D.C. (16) 10         H.sub.2 O.sub.2                                                                     50 6%                                                                               12  B 95 light bronze                  C.sub.10                                                                          (15)                                                                              2.5                                                                   A 13                                                                              C.sub.11                                                                          (17)                                                                              0.40                                                                              D.C. (16) 10         H.sub.2 O.sub.2                                                                     50 6%                                                                               5.5 D    Prussian blue              A 14                                                                              6     0.50                                                                              MM/SM/DM (18)                                                                            2.5                                                                               Ethanol                                                                              30          7.5 D    turquoise blue             A 15                                                                              C.sub.7                                                                           (12)                                                                              0.50                                                                              VP/VA 30/70                                                                              2  Ethanol                                                                              40          10  D    very dark gray with           C.sub.12                                                                          (19)                                                                              0.30                                                                              (22)                                    violet glints                 C.sub.13                                                                          (20)                                                                              0.20                                                                     C.sub.14                                                                          (21)                                                                              0.05                                                                  A 16                                                                              3     0.75                                                                              VA/CA (23)                                                                     M.W. = 50,000                                                                            1  Ethanol                                                                              20          8.1 D    blue gray                  A 17                                                                              5     0.33                                                                              VA/CA (23)                              silvery gray with                      M.W. = 10,000                                                                            2  Ethanol                                                                              50          10.5                                                                               B95  mauve glints               A 18                                                                              2     0.02                                                                              VP/VA 70/30                                                                              3  Ethanol                                                                              25          8.6 D    pearly mauve pink                      (24)                                                               A 19                                                                              21    0.6                                                                               VP/VA 70/30                                                                              3  Ethanol                                                                              25          9   D    wild rose pink                         (24)                                                               A 20                                                                              9     0.25                                                                              VP/VA 60/40                                                                              2  Isopropanol                                                                          35          8   D    very luminous mauve                    (25)                                                               A 21                                                                              18    0.25                                                                              VP/VA 30/70                                                                              2  Ethanol                                                                              40          7.5 D    pearly pale blue                       (22)                                                               A 22                                                                              22    0.3                                                                               VA/CA (23)                                                                     M.W. = 70,000                                                                            1  Ethanol                                                                              36          4.5 D    silvery light gray         A 23                                                                              19    0.75                                                                              "Gafquat 734"                                                                            2  Isopropanol                                                                          20          10  D    golden beige                           (26)                                                               A 24                                                                              12    0.25                                                                              MA/MVE (27)                                                                              1  Ethanol                                                                              45          8.5 D    pearly very light                                                              green                      A 25                                                                              10    0.5                                                                               PVP (28)  2  Isopropanol                                                                          35          7   D    silvery light                                                                  blue                       A 26                                                                              14    0.5                                                                               VA/AS/AA (29)                                                                            2.5                                                                               Ethanol                                                                              50          10  D    deep parme                 A 27                                                                              8     0.25                                                                              VA/AS/AA (29)                                                                            2.5                                                                               Ethanol                                                                              50          7.5 D    luminous silvery                                                               violet                     A 28                                                                              11    0.35                                                                              VA/AS/AA (29)                                                                            2.5                                                                               Ethanol                                                                              50                                                                               PA (30)                                                                              5 2%                                                                               10  D    pink                       A 29                                                                              13    0.55            EMDE (31)                                                                             8                                                                               H.sub.2 O.sub.2 (32)                                                                40 6%                                                                               11  B 95 pink golden beige          A 30                                                                              16    2  CMC (10)  5  Ethanol                                                                              20          11  D    pale pink with                                                                 golden glints              A 31                                                                              15    1  D C (16)  8  Ethanol                                                                              20                                                                               H.sub.2 O.sub.2                                                                     25 6%                                                                               10.5                                                                               D    slightly mauve pink        A 32                                                                              17    0.75                                                                              LSA (33)  5          H.sub.2 O.sub.2                                                                     50 6%                                                                               10  D    slightly pink light                                                            blond                      A 33                                                                              20    0.75                                                                              LSS 19    20                   10.3                                                                               D    silvery lavander                                                               blue                       __________________________________________________________________________      (1) PU = urea peroxide (lbis).sub.D = bleached hair                            (2) Cl = 2-methoxy-4-hydroxy-4'-N,N-dimethylamino diphenylamine                (3) C2 = nitroparaphenylenediamine                                             (4) AL 10.5 OE = Lauryl alcohol oxyethylenated with 10.5 moles of              ethyleneoxide                                                                  (5) LSS 19 = mixture of 19% of lauryl alcohol oxyethylenated with 2 moles      of ethyleneoxide and 81% of the sodium sulfate salt of this same               oxyethlenated alcohol                                                          (6) EDTA = ethylene diamine tetra-acetic acid                                  (6a) C.sub.3 = 2,4-diamino anisole dihydrochloride                             (7) C.sub.4 = methoxy p-phenylenediamine dihydrochloride                       (8) C.sub.5 = paraaminophenol                                                  (9) C.sub.6 = nitro-orthophenylenediamine                                      (10) CMC = Carboxymethylcellulose                                              (11) B 95 = 95% naturally white hair                                           (12) C.sub.7 = 3,5-dimethyl-4-hydroxy-4'-N,N-dimethylamino diphenylamine       (13) C.sub.8 = 2-acetylamino-4-hydroxy-4'-N,N-dimethylamino diphenylamine      (14) C.sub.9 = 3-methoxy-4,6-diamino-4'-hydroxy diphenylamine                  dihydrochloride                                                                (15) C.sub.10 = 2-amino-4-methoxy phenol                                       (16) DC = diethanolamides of fatty acids of coprah                             (17) C.sub.11 = 2-methoxy-4-hydroxy-4'-N,N-dimethylamino diphenylamine         (18) MM/SM/DM =  Terpolymer of methyl methacrylate (15-25%), stearyl           methacrylate (25-35%) and dimethylaminoethyl methacrylate (52-62%)             quaternized by dimethyl sulfate                                                (19) C.sub.12 = N-[4'-(hydroxy) phenyl] 2,6-dimethyl benzoquinoneimine         (20) C.sub.13 = 1-N-methylamino-4-N'-γ-aminopropylamino                  anthraquinone                                                                  (21) C.sub.14 = nitrometaphenylenediamine                                      (22) VP/AV 30/70 = Copolymer of vinylpyrrolidone/vinyl acetate 30/70, M.W      = 160,000                                                                      (23) VA/CA = copolymer of vinyl acetate/crotonic/acid 90/10                    (24) VP/VA 70/30 = Copolymer of vinylpyrrolidone/vinyl acetate, 70/30 M.W      = 40,000                                                                       (25) VP/VA 60/40 = Copolymer of vinylpyrrolidone/vinyl acetate, 60/40          having a viscosity of 3.3 to 4 cps at 250° C in a 5% ethanol            solution                                                                       (26) Quaternary copolymer of polyvinylpyrrolidone having a molecular           weight of about 100,000, sold under the mark "Gafquat                          (27) MA/MVE = Monobutyl ester of the copolymer of maleic anhydride             methylvinylether,1:1, having a specific viscosity of 0.1 to 3.5 measured       at 25° C at a concentration of 1% in methylethylketone                  (28) PVP = Polyvinylpyrrolidone M.W. = 40,000                                  (29) VA/AS/AA = Terpolymer of vinyl acetate/allyl                              stearate/allyloxyacetic/acid 80.5:15:4.5                                       (30) PA = ammonium persulfate                                                  (31) EMDE = monomethyl ester of diethylene glycol                              (32) H.sub.2 O.sub.2 = hydrogen peroxide                                       (33) LSA = ammonium lauryl sulfate                                        

What is claimed is:
 1. A composition for coloring keratinic fibers comprising in an aqueous or hydroalcoholic solution an effective amount of at least one diphenylamine compound of the formula. ##STR6## wherein R₁ and R₄ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl containing 1-6 carbon atoms, lower alkoxy containing 1-6 carbon atoms, amino, lower alkyl amino wherein the alkyl moiety has 1-6 carbon atoms, acetylamino, lower carbamylalkyl amino wherein the alkyl moiety has 1-6 carbon atoms, lower hydroxyalkyl amino wherein the alkyl moiety has 1-6 carbon atoms, lower carbalkoxy amino wherein the alkoxy moiety has 1-6 carbon atoms and ureido;R₂ and R₃ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl containing 1-6 carbon atoms, lower alkoxy containing 1-6 carbon atoms, acetylamino and ureido; R₅ and R₈ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl containing 1-6 carbon atoms and lower alkoxy containing 1-6 carbon atoms; and R₆ and R₇ represent lower alkyl having 1-6 carbon atoms; or a salt thereof.
 2. The composition of claim 1 wherein said diphenylamine is a salt.
 3. The composition of claim 1 wherein said diphenylamine is present in an amount of about 0.002 to 5 percent by weight of said composition.
 4. The composition of claim 1 having a pH between about 4.5-12.
 5. The composition of claim 1 which also includes a direct hair dye.
 6. The composition of claim 1 which also includes a member selected from the group consisting of an oxidation dye and a coupler.
 7. The composition of claim 6 wherein said oxidation dye is selected from the group consisting of orthophenylenediamine, paraphenylenediamine, orthoaminophenol and paraaminophenol.
 8. The composition of claim 6 wherein said coupler is selected from the group consisting of metadiamine, metaaminophenol, metaacetylamino phenol and metadiphenol.
 9. The composition of claim 6 wherein said oxidation dye is a benzene compound carrying 3-4 substituents selected from the group consisting of hydroxy, amino and methoxy.
 10. The composition of claim 1 which also includes a member selected from the group consisting of another diphenylamine, leuco-indophenol and leuco-indamine.
 11. The composition of claim 1 which also includes a dye selected from the group consisting of a nitrobenzene dye, an azo dye, an anthraquinone dye, an indamine, an indophenol and an indoaniline.
 12. The composition of claim 1 which also includes a member selected from the group consisting of a glycol and a wetting agent.
 13. The composition of claim 1 which is a hydroalcoholic solution and also includes at least one cosmetic film-forming resin.
 14. The composition of claim 13 wherein said hydroalcoholic solution is an aqueous solution of a low molecular weight alcohol.
 15. The composition of claim 14 wherein said alcohol is selected from the group consisting of ethanol and isopropanol.
 16. The composition of claim 14 wherein said alcohol is present in an amount of about 20-70 weight percent.
 17. The composition of claim 13 wherein said cosmetic film-forming resin is present in an amount of 1-3 weight percent.
 18. The composition of claim 13 wherein said cosmetic film-forming resin is selected from the group consisting of polyvinylpyrrolidone, a copolymer of vinyl pyrrolidone and vinyl acetate, a copolymer of vinyl acetate and crotonic acid, a copolymer of maleic anhydride and butyl vinyl ether, a terpolymer of methyl methacrylate, stearyl methacrylate and dimethylaminoethyl methacrylate quaternized by dimethyl sulfate and a terpolymer of vinyl acetate, allyl acetate and allyloxy acetic acid.
 19. The composition of claim 1 in the form of a cream, a gel or an aerosol.
 20. The composition of claim 1 which also includes an oxidizing agent.
 21. The composition of claim 20 wherein said oxidizing agent is selected from the group consisting of hydrogen peroxide, ammonium persulfate and urea peroxide.
 22. A process for dyeing keratinic fibers comprising impregnating said fibers to be dyed with an effective amount of the composition of claim 1, permitting said composition to remain in contact with said fibers for a period ranging from about 5 to 30 minutes, rinsing said fibers and drying said fibers.
 23. The process of claim 22 wherein said fibers are living human hair and said hair after rinsing is shampooed prior to drying the same.
 24. A process for coloring human hair comprising applying to previously washed and rinsed hair an effective amount of the composition of claim 13, rolling the hair on curlers and drying the hair. 